JPS6261633B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a water- and oil-repellent treatment composition that improves stains left behind when used on textiles, clothing, etc. Various water repellents are used to impart water repellency to textiles, clothing, leather, etc., but fluorine-based water and oil repellents have superior water repellency compared to silicone-based water repellents. It has recently been widely used as an aerosol type because it has the advantages of being easy to clean, fast-acting, and effective in small amounts, and is also oil-repellent, so it can be expected to have an antifouling effect. However, if an aerosol containing a fluorine-based water and oil repellent is sprayed onto clothing, or a solution of the water and oil repellent dissolved in a solvent is applied to clothing, white stains may appear on the clothing after the solvent evaporates. There is a disadvantage that it occurs. Particularly when clothing has a dark color such as black or navy blue, white stains are noticeable and seriously impair the appearance. Conventionally, organic solvents have been investigated to improve the appearance of stains, and 1,1,2-trichloro-
Although 1,2,2-trifluoroethane is said to be preferable as a solvent for fluorine-based water and oil repellents, it does not completely solve the problem of remaining stains.
Further, if mineral turpentine, which is a petroleum-based solvent, is used, the stain residue can be considerably improved, but since mineral turpentine has a high boiling point, it takes a long time to evaporate, which is undesirable. As a result of repeated research in order to solve the above-mentioned drawbacks, the present inventors have found that stain retention can be significantly improved by blending a specific esterified product with a fluorine-based water and oil repellent and a chlorinated solvent. The present invention has now been accomplished. That is, the present invention uses fluorine-based water and oil repellents from 0.05 to
A di-lower alkyl ester of dicarboxylic acid having 4 to 10 carbon atoms, a tri-lower alkyl ester of citric acid and 4 to 10 carbon atoms to a mixed stock solution consisting of 5% by weight and 99.95 to 95% by weight of a chlorinated solvent. A composition for water and oil repellency treatment characterized by containing one or more esters selected from the group of lower fatty acid esters of dihydric alcohols. The fluorine-based water and oil repellent in the present invention is a polymer of a perfluoroalkyl group or a polymerizable monomer having a fluoroalkyl group, or a copolymer of the monomer and other monomers, and is usually commercially available. Fluorine-based water and oil repellents can also be used as they are. Among these, polymers of the formula () or () or copolymers of these and the formula () are preferred. R ^f R ¹ OCOC (R ² ) = CH ₂ ... () R ^f SO ₂ N (R ³ ) R ¹ OCOC (R ² ) = CH ₂
...() (wherein, R ^f is a perfluoroalkyl group having 3 to 20 carbon atoms, R ¹ is an alkylene group having 1 to 8 carbon atoms,
R ² is hydrogen or methyl group, R ³ is hydrogen or carbon number 1
〜3 represents a rukyl group. ) R ⁴ OCOC (R ⁵ )=CH ₂ ... () (In the formula, R ⁴ is an alkyl group having 3 to 28 carbon atoms, R ⁵
represents hydrogen or methyl group. ) Furthermore, monomers represented by the general formula () or () and fluoroalkyls such as acrylonitrile, methacrylonitrile, ethylene, vinyl acetate, styrene, butadiene, and chloroprene, instead of or together with the monomers represented by the general formula (). A copolymer of one or two monomers having no group can also be used. By copolymerizing these monomers that do not have a fluoroalkyl group, it is possible to appropriately improve properties such as durability, flexibility, and feel in addition to water and oil repellency and dirt releasability. In addition to using one type of polymer as the water and oil repellent, it is also possible to use a mixture of two or more types of polymers having different content ratios of fluoroalkyl groups. For example, a copolymer of general formulas () and () and a copolymer of general formulas () and () may be mixed and used. The amount of the fluorine-based water and oil repellent is 0.05 to 5% by weight, preferably 0.3 to 2% by weight. Compounding amount is 0.05% by weight
If it is less than 5% by weight, sufficient water and oil repellency cannot be obtained.
This is because, if the amount exceeds 100%, the solubility in chlorinated solvents will decrease, and the texture of the object to be treated will deteriorate or whitening will occur. As the chlorinated solvent in the present invention, chlorinated hydrocarbon solvents and Freon solvents are used, and specifically, dichloromethane, 1,2 dichloroethane,
1,1,1-trichloroethane, trichlorethylene, perchlorethylene, Freon 112 (S-
(Tetrachlorodifluoroethane), Freon 113
(1,1,2-trichloro-1,2,2-trifluoroethane) is shown. Among these, dichloromethane, 1,1,1-trichloroethane, Freon 112, and Freon 113 are preferred from the viewpoint of usability. The blending amount of the chlorinated solvent is 95 to 99.95% by weight, preferably 98 to 99.7% by weight. In the present invention, the blended stock solution consisting of the fluorine-based water and oil repellent and the chlorinated solvent has a carbon number of 4 to 10.
At least one esterified product selected from the group of diesters of dicarboxylic acids and lower alcohols, trilower alkyl esters of citric acid, and esters of dihydric alcohols having 4 to 10 carbon atoms and lower fatty acids. be. The lower alkyl group and lower fatty acid in these esterified products usually have 1 to 5 carbon atoms, preferably 1 to 4 carbon atoms. Furthermore, as the fatty acid ester of dihydric alcohol having 4 to 10 carbon atoms, mono- or diesterified products can be used. Specifically, these esterified products include dimethyl succinate, diethyl succinate, dibutyl succinate, diisobutyl succinate, dimethyl adipate, diethyl adipate, dibutyl adipate, diisobutyl adipate, dibutyl phthalate, dipropylsuberate, dibutyl suberate, diethyl Sebacate, dipropyl sebacate, dibutyl sebacate, diisobutyl sebacate, triethyl citrate, butylene glycol monoacetate, butylene glycol diacetate, butylene glycol dipropionate, butylene glycol divalerate, hexylene glycol diacetate, hexylene Examples include glycol dipropionate. Among these, diesters of dicarboxylic acids selected from the group of succinic acid, adipic acid, suberic acid and sebazic acid and alcohols selected from the group of methanol, ethanol, propanol, butanol and isobutanol are preferred from the viewpoint of odor. The amount of the esterified product to be blended is appropriately selected depending on the amount of the fluorine-based water and oil repellent in the blended stock solution consisting of the fluorine-based water and oil repellent and the chlorine-based solvent, but preferably in 100 parts by weight of the blended stock solution. The amount is 0.001 to 5 parts by weight, particularly preferably 0.01 to 1 part by weight. In this way, by adding a specific esterified product to the blended stock solution, it is possible to significantly improve the appearance of stains, and adding ethyl alcohol or ethylene glycol instead of this product will not produce an effect comparable to that of the product of the present invention. do not have. The composition for water and oil repellency treatment of the present invention can be used as a solution by applying it directly to an article to be treated or by dipping a cloth to be treated, but after preparing the composition for water and oil repellency treatment, a propellant can be used. It can be easily made into an aerosol and used by adding it and filling it into a container. Propellants used in this case include LPG, propane, butane, dichlorodifluoromethane (Freon 12), fluorotrichloromethane (Freon 11), dichlorotetrafluoroethane (Freon 114), dimethyl ether, CO ₂ , N ₂ O, etc. It is possible. The blending ratio of the product of the present invention and the propellant is 99/1 to 30/70 (wt%), preferably 97/3 to 50/50 (wt%). The water- and oil-repellent treatment composition of the present invention can be used on articles to be treated in any manner depending on the form of use (solution type, aerosol type, etc.) and the type of article to be treated.
The aerosol type is easy to use because it is sufficient to simply spray it onto the object to be treated, and is therefore particularly suitable as a mode of use for the product of the present invention. The water and oil repellent treatment composition of the present invention further includes a small amount of a silicone water repellent, an insect repellent, an antistatic agent,
A flame retardant can be added. According to the product of the present invention, natural fibers such as wool, cotton, and silk, regenerated fibers such as rayon and Kyupra, semi-synthetic fibers such as acetate and triacetate, synthetic fibers such as polyester, polyamide, polyacrylonitrile, polypropylene, and polyvinyl chloride; These mixed fibers and fabrics, clothing, glass fibers, asbestos fibers, glass, paper, wood, leather,
fur, brick, cement, metal, plastic,
It leaves no stains on plaster and can impart excellent water and oil repellency. At this time, an antifouling effect is also exhibited as an effect of imparting oil repellency. The product of the present invention has good compatibility with the propellant Freon, so it is particularly suitable for aerosolization, and has quick drying properties. Next, the present invention will be explained in detail with reference to Examples. In the following examples, water repellency, oil repellency, and stain retention were evaluated by the following methods. Γ Water repellency JIS-
Evaluation was made by spraying L-1092. The evaluation criteria are shown in Table-1.

[Table] Γ Oil repellency Compositions of n-heptane and nujiol in various mixing ratios were dropped onto a test cloth (Wool Tropical), and oil repellency was determined based on the liquid composition that could hold the droplets for 3 minutes or more. Table 2 shows the evaluation criteria for oil repellency.

【table】

[Table] Γ Stain Remains The water and oil repellent treatment composition was sprayed on black wool tropical, and after hanging to air dry, the state of stain occurrence was judged according to the criteria shown in Table 3.

[Table] Example 1 (A) Various additives (Table-
Added 0.5 part by weight of 4)

[Formula] Water and oil repellent consisting of a copolymer of C ₈ H ₁₇ OCOCH=CH ₂ 0.5% by weight 1,1,1-trichloroethane 99.5% by weight (B) Propellant (Freon 12/Freon 11=6/ 4) An aerosol water and oil repellent treatment composition consisting of (A)/(B)=85/15 (weight ratio) was produced and its performance was evaluated. The results are shown in Table 4.

[Table] From Table 4, it can be seen that the product of the present invention can significantly improve stain retention without reducing the water- and oil-repellent effect. Example 2 When the performance of the following various water and oil repellent treatment compositions was evaluated, all compositions showed water repellency to Wool Tropical of 90 or higher, oil repellency of 120 or higher, and stain retention of 4 or higher. The value was shown.
Regarding Composition 3, the undiluted solution was added at 5% per 30 x 30 cm of cloth.
The performance was evaluated by applying g. Composition 1 (A) 0.2 parts by weight of diisobutyl adipate was added to 100 parts by weight of the stock solution below. (Blended stock solution) 8/2 copolymer of C ₈ F ₁₇ CH ₂ CH ₂ OCOCH=CH ₂ and C ₄ H ₉ OCOCH=CH ₂
1% by weight Freon 113 56% by weight 1,1,1-trichloroethane 43% by weight (B) Propellant (Freon 12/LPG = 6/4) (A)/(B) = 82/18 (weight ratio) Aerosol water and oil repellent treatment composition. Composition 2 (A) 0.3 parts by weight of triethyl citrate was added to 100 parts by weight of the stock solution below. (Blend stock solution) C ₈ F ₁₇ CH ₂ CH ₂ OCO (CH ₃ ) 4/1 copolymer of C=CH ₂ and CH ₂ = CHCONHCH ₂ OC ₄ H ₉ 0.6% by weight 1,1,1-trichloroethane 25 Weight % Freon 112 22.4 weight % Freon 113 52 weight % (B) Propellant (LPG) (A)/(B)=75/25 (weight ratio) An aerosol water and oil repellent treatment composition. Composition 3 Add diethyl sebacate to 100 parts by weight of the stock solution below.
A water and oil repellent treatment composition containing 0.2 parts by weight. (Blended stock solution) 6/4 copolymer of F ₂ HC (CF ₂ ) ₅ SO ₂ NH (CH ₂ ) ₃ OCOCH=CH ₂ and C ₄ H ₉ OCOCH=CH ₂
0.4% by weight 1,1,1-trichloroethane 49.8% by weight Dichloromethane 49.8% by weight

Claims (1)

[Scope of Claims] 1. In a blended stock solution consisting of 0.05 to 5% by weight of a fluorine-based water and oil repellent and 99.95 to 95% by weight of a chlorinated solvent, 4
One or more types selected from the group of di-lower alkyl esters of dicarboxylic acids having ~10 carbon atoms, tri-lower alkyl esters of citric acid, and lower fatty acid esters of dihydric alcohols having 4-10 carbon atoms. A water- and oil-repellent treatment composition characterized by containing an esterified product. 2. The composition according to claim 1, wherein the lower alkyl group and the lower fatty acid in the esterified product have carbon numbers in the range of 1 to 5. 3 A di-lower alkyl ester of a dicarboxylic acid having 4 to 10 carbon atoms is selected from the group of succinic acid, adipic acid, suberic acid and sebacic acid and a dicarboxylic acid selected from the group of methanol, ethanol, propanol, butanol and isobutanol. The composition according to claim 1, which is a diesterified product with an alcohol. 4 The content of esterified products is per 100 parts by weight of a blended stock solution consisting of a fluorine-based water and oil repellent and a chlorinated solvent.
The water and oil repellent treatment composition according to any one of claims 1 to 3, wherein the amount is in the range of 0.001 to 5 parts by weight.